Process of treating emulsions



Oct. 11, .1938.

S. E. CAMPBELL.

PROCESS OF TREATING EMULSIONS Filed Sept. 16, 1935 2 Sheets-Sheet 1 NaCl COGL rah/ER f/v VEN TOR Jammer 6. [ampc mex Oct. 11, 1938. s. E. CAMPBELL 2,133,185

PROCESS 0F TREATING EMULSIONS Filed Sept. 16, 1935 2 Sheets-Sheet 2 E Heat EXC/m12? er 9;; any' Sfar@ e E/a/oofator [Valeo/*afar /7 )ff/7 for .Sama er ff fampe maar e... n, '193e l 2,133,186

UNITED STATE-s 4PATENT OFFICE PliocEss oF TREATING EMULsIoNs Sumner E. Campbell, Long Beach, Calif. Application september 1c, 1935, seriai No. 40,721 claims. (o1. 19e-4) This invention relates to a process for breaking or brine, of a degree ci salinity at least that of emulsions and has for its principal object the the water in the entering emulsion, and the towseparation of water from emulsions, such as are er I4 and contained contact material and soluknown as crude oil emulsions or emulsions retion are 'primarily heated to the desired tem- 5 sulting in the production of crude oils from the perature of the emulsion to be treated, say about 5 earth, or otherwise. 200 F. by means of a steam coil I6 before the In dehydrating crude oil, or other oil containemulsion is flowed into` tower I4. ing water generally dispersedin large or small The emulsiiied oil at a temperature of about particles therein, many methodsare in vogue for 200 F. is Yilowed upwardly through the iinely `separating the water successfully and economi- 1 divided and heated contact material I5 immersed lo cally, yet such methods often fail to break soin brine of a predetermined degree of salinity, called tight emulsions except at a prohibitive` said contact inaterial being held firmly in place cost. i by a perforated screen, or plate, I1 and on en- Crude petroleum as normally produced from tering the bottom of tower I4 is distributed van oil well is mixed with varying percentages of through a plate I8 and thence through the con- 15 water, usually saline in character, and the salintact J material I5 wherein the normally spherical ity of such associated water varies considerably globules of oil with entrained water are distorted depending on the locality from which the oil is innumerable times in their upward passage produced. through the tower whereby the enveloping emul- For instance., Water separated from certain sifying jacket around the water is ruptured ex- 2f) vcrude oils in the Signal Hill fleldlin California posing the inner parts of the oil globule to conhas a salinity of about from three to six pertact with-the body of saline water in which the cent, and in the present process such oils are contact material is immersed and coalescence of heated according to the following disclosure to the water globules with said body of water is acpractically remove substantially all the water complished. 25

e from the oil, or at least to remove the/water to I, 'I'he result from this mode of operation is disa degree in which it is practically ready for retinct from agglomeration wherein, due to surface iining or other purposes. ,tension eifects, the particles of water may be built In the diagrammatic sheets of drawings: up by accretion on loosely packed and large size Fig. 1 is a flow sheet illustrating the preferred contact material particles to a point where they 30 method of operation. become large enough to separate from the oil by l Fig. 2 is avertical sectionalwview of a treating -gravity'.

tower used in Fig. 1. At a predetermined level in tower I4 there is Fig. 3 is a ow sheet showing a modication of arranged an overow drain for the coalesced wa- Fig. 1. ter which is illustrated for clarity in the form of 35 Fig. 4 illustrates a modiilcation. a wide mouthed funnel I9 connected with a The crude oil, or other emulsied oil, may be valved drain pipe 20 passing out of the bottom of stored in tank I0 from which large masses of watower I4 and a liquid level of coalesced water ter easily separable by gravity are withdrawn X-X is maintained which is slightly above the 40" through pipe Il. horizontal plane of the upper edge of the funnel 40 The emulsifled oil is then drawn off by pump I 2 I9, the object being to assure withdrawal only and fed through heater I3, which may be an of coalesced water through pipe 20. ordinary heat exchanger heated by steam or a It is, of course, clear that any other suitable still such as a pipe still or the like in which liquid draw-olii can be used in place of funnel I9 the temperature of the emulsion is raised to and that pipe 20 may be equipped with a' valve 45 about 200 F. The heated mixture is then passed 2l, either manually operated or of a well known into the bottom of a tower I4, the height of which automatic type to maintain the liquid level X-X.

is about three to four times its diameter,` which In some cases "only one such tower I4 is reisabout three-fourths oiled with a nnely divided quired. but a plurality 0f such towers in series inert contact material I5 such as quartz or the is .within the scope of the invention if necessary 50 like. No. 16 mesh silica will serve the purpose for any reason. I

very well.` It is highlyI desirable to maintain the salinity 'I'he tower` I4, thus packed with contact mateof the body of water held in tower I4 up to the rial-I5, is lled to slightly above the upper surpoint of saturation in order to effect the most face of the packing material with a salt solution.4 complete separation of the water from the oil, but 55 the process is emcient in most cases with a salinity of about ten percent In such cases where the salinity of the entering water is suihcient to maintain the desired salinity of the body of water in tower i6 that is sucient, but if the salinity of the entering water decreases below the necessary concentration, a

concentrated NaCl, or other equivalent brine, solution is added to the emulsied oil prior to its entry into tower i6 from a brine tank 22.

' The process is continuous and theintroduction of the salt solution may also be continuous while the pressure may be just sumcient to assure a desired flow rate or may be fromI 50 to 100 pounds per square inch above atmospheric pressure, which increased pressure aids in breaking the emulsion while preventing excessive volatilization of.desred light products at the operating temperatures. .l

While a temperature of 200 F. is noted as an eincient temperature at substantially atmospheric pressures, it must be understood that the teml perature may range from 150 to 350 F., depending on type of emulsion and corresponding 4pressure used.

The dehydrated oil passes, if necessary, through a second similar contact tower 25 and, when volatile compounds are given 0E from the towers i4 and 25 at the operating temperatures they may be either vented through a pipe 26 to atmosphere, or used as fuel or for other purposes, or

may be passed through line 27 and cooler 28 to a crude oil storage tank 29 to which the dehydratedoil is led from tower 25 through line 30 passes into vtower I6, as described, in which a` body of contact material and a body \of water of any degree -of salinity is maintained wherein the bulk of the free water is eliminated. f

The oil, still containing iinely divided particles of water of a low degree of salinity then passes into similarly constructed tower 25 in which the y, contact material is salt so that the water dissolves suihcient of the salt to provide a high -saline concentration and eiciently separate'the remaining water.

Another alternative method is shown in Fig. 1 in which at times the wet oil in storage tank I0 contains a large percentage of water which is below the salinity required for efilcient separa.' tion and in which case the addition of concentrated brine from tank 22 would be inexpedient.

The procedure in such event is to pass the heated oil through line 67 into a tower 48 (similarly constructed to tower i4) and containing a somewhat concentrated brine solution of about 23% in which the bulk of the water is removed. v

'I'he mixing of excess water with the brine in tower 48 so far reduces its salinity that tower into tower 50 (similarly constructed and oper- Example No. 1

' `B. S. B. S. B. S Temp. Temp. Temp. and and and Time in out out Water Water Water No. 48 No. 48 No. 50 in out out No. 48 No. 48 No. 50

PF. 1". F. Percent Percent Percent*v 3:30 p. 200 176 167 3. 0 0. 6 0. 2 3:55 p. 204 181 168 2 4 0. 4 0. 1 5:00 p. 200 166 162 3. 4 0. 3 0. 1 6:00 p. 198 158 150 2. 8 0. 2 0. 1 7:00 p. 204 165 145 2. 5 0. 3 0. 1 8:00 p. 202 167 138 3. 2 0.3 0. 1 9:00 p. 202 169 136 2.8 0. 5 0. 1 10:00 p. 200 179 140 2. 8 0. 5 0. 1 11:00 p. 201 183 143' 2. 8 0.4 0. 1 12:00 p. 202 184 144 2. 7 1. 1 +0.11 1:00 a. m 202 187 152 2. 9 1. 2 0. 2 2:00 a. m- 200 186 154 3` 4 1. 4 +0. 1 3:00 a. m- 200 183 151 2.7 1. 1 0. 1 4:00 a. m- 204 184 154 3. 6 0. 9 0. l 5:00 a. m- 202 179 153 2. 0 l. 0 0. 2 6:00 a. m- 198 179 150 1. 5 l. 0 0. 2 7:00 a. m- 199 176 144 1. 9 1. 2 l0. 2 8:00 a. m- 199 180 148 1. 6 1. 4 -0. 2 9:00 a. m- 205 i 173 145 4. 6 1. 8 0. 1 10:00 a. m 192 183 147 1. 6 1. 2 0. 1 11:00 a. m 199 178 144 1. 2 0. 8 0. 1 12:00 m. 206 170 140 1. 8 1. 4 -0. 1 1:00 p. n1- 200 174 144 1.8 1. 6 -0. 1 2:00 p. m- 193 182 143 1.8 1.6 -0. 1 3:00 p. m 196 178 143 2.0 1. 5 -0. 1 4:00 p. m- 200- 144 128 12. 6 0. 2 0. 1 5:00 p. m- 200 144 138 8. 4 0. 2 0. 2 6200 p. in; 196 135 134 13. 0 0. 3 l 0. 1 7:00p. m- 200 142 134 9. 6 0. 2 0. 1 8:00 p. mm0 160 1% 8. 6 0. 4 0. 1 9:00 p. m 198 150 114 9. 2 0. 3 0. 1 10:00 p. m 200 150 110 12. 6 0. 3 0. 1 11:00 p. m 218 153 109 12.0 0. 3 0. 2 12:00 p. m 203 157 110 12. 2 0. 4 0. 1 1:00 a. ln- 198 173 112 12. 6 0. 5 0. 1 2:00 B. 111 2l) 175 114 9.8 0. 5 0. 1 3:00 a. m 199 176 116 7.8 0. 5 0. 1

Example No 2 4:00 a. m 202 175 122 56.0 0 5 0 1 5:00 a. m 197 174 126 38. 0 0 9 0. 1

Example No. 3

12:00 p. m 200 144 128 12.6 0. 2 0. 1 1:00 a. m- 200 144 138 8. 4 0. 2 0. 2 2:00 a. m 198 135 134 13.0 0. 3 0. l 3:00 a. mm0 142 134 9. 6 0. 2 0.1 4:00 a. m- 200 160 128 8. 6 0. 4 0. 1 5:00 a. m- 198 150 114 9. 2 0. 3 0. 1 6:00 a. m- 2(1) 150 110 12. 6 0.3 0. 1 7:00 a. m- 2H 153 109 12. 0 0. 3 0. 2 8:11) a. m- 203 157 110 12. 2 0. 4 0. l 9:00 a. m- 198 173 112 12. 6 0. 5 0. l 10:00 a. ln 200 175 114 9. 8 0. 5 0. 1 11:00 a. m 199 176 116 7.8 0. 5 0:1

Example No.11 is `a mixture of crudes which had already been treated with chemical dehydrating agents which had failed to reduce the water content to the required commercial limit for pipe line oil whichis from 1 to 3%.

A modication is shown inv Fig. 3 in which the emulsied cold oil is passed from storage 32 by 'pump' 33 and line 34 through heat exchanger 35 in which its temperature is somewhat raised and then through line 36 and heater 31 wherein its temperature is brought to the desired point, as before described, of the o rder of 200 F,

The thus heated emulsion then ows under the required applied pressure, superatmospheric or otherwise, through line 56 to the bottom of tower arcaica 38, `which is similarly` constructed to tower I4 before described, and upwardly through the contact material therein.`

At the temperatures employed under these conditions, some of the water is carried with the oil stream in the form of a fog so that complete separation in one tower is not possible.

If. now, such heated emulsied oil is run through a system such as shown inFig. 3, this diiiculty of complete separation of the oil and water is overcome.

More specifically, this is accomplished by iirst passing emulsied oil, crude or otherwise, while heated to a desired temperature through a first contact section wherein the bulk of the water is separated and is then cooled to at least atmospheric temperature prior to passage through a Vsecond contact section whereby the moisture in the form of a fog is first reduced by cooling to minute particles of water whichAare coalesced and separated in the second or succeeding contact sections. A further advantage accrues from this mode of operation by conservation of valuable light constituents of the oil which otherwise may be lost by evaporation if carried over with hOt 011. 1

The thus heated oil is passed into the bottom of tower t9, which is preferably insulated and A contains contact material substantially immersed in a maintained body of the heavier liquid to be removed. In tower 39 at relatively `high temperature and relatively low velocity, the bulk of the water is separated and removed from the oil, which then passes through heat exchanger 35 wherein it givesup a large percentage of its applied heat to the cold wet oil and iiows through a cooler di wherein its temperature is reduced to atmospheric' temperature, or any desired lower temperature above the freezing point of water.

The thus cooled oil, which will then contain the aforesaid fog in the form of minute particles of water, passes upwardly through a second similar contact tower 82 containing contact material similarlyimmersed in a body of the heavier liquid to be removed wherein said minute particles of water are coalesced and separated.

In the breaking of certain crude oil emulsions, it may be desirable to add certain chemicals to the oil in order to change surface tension conditions and such chemicals may be passed into the oil before contact as, for instance, through pump 45 and mixer 86.

Another modification is shown in Fig. 4 in which the cold wet oil from storage 52 is picked up by pump 53 and passed through heat exchanger 54 in which it receives heat from the treated oil and then ows through a heater 55, receiving steam'from supply pipe 56 to acquire the desired temperature of say 200 F. and goes thence through line 51 to the bottoin of a contact tower 58.

Tower 58 includes a lower contact and coalescing section 59 iilled to its discharge level with a concentrated brine solution of say about 23% salinity and containing similarly disclosed contact material 88 supported on perforated plate 6i and having a discharge section 62 closed by a perforated screen 63 surmounted by a baliie4 64.

The liquids discharged from section 62 flow into a zone of low velocity 65 the bottom of which consists of a launder, to permit separation of saline water by gravity which is continuously withdrawn in any well known manner through pipe 66 to maintain a desired constant level o water in launder 65.

The oil owing upwardly through zone 65, in which separation of the bulk of the water takes place, iiows into an, upper coalescing section 61 through a pipe 68,` surounded by a downiiow pipe 68 into which it is directed downwardly by a baille 10, thence through a plurality of perforated radial distributing arms 1I at the bottom of similarly describedcontact material 12. Section 61 has a discharge neck 13 closed by a perforated screen 14 surmounted by a. baille 15.

Section 61 is primarily iilled with a concentrated brine solution of say about 23% salinity to the level of discharge from neck 13 through which the liquids flow to launder 16 in which, due to decreased velocity of iiow the remaining water is separated by gravity from the oil, the oil passing through line 18, heat exchanger 54 and cooler 19 to storage.

Manholes 80, 8|, 82 and 83 are provided for llingand emptying sections 59 and 61 with contact material.

The modification of Fig. 4 has two especial advantages. The iirst is that when the water contained in the oil has a low degree of salinity so as to reduce the concentration of the contained body of saline water in lower section 59 below an eflicient concentraiton, such lowered concentration maybe increased by introducing a more highly concentrated saline solution from the upper coalescing section 61 `while maintaining a highly concentrated solution in section 61.

This is accomplished by passing a concentrated saline solution oi' say about 23% to 25% salinity through pipe 88 into pipe 69 to be de- Tiected by baille 18 and iiow concurrently with the partially dehydrated oil into section 61. In this manner,y suspended particles of water of relatively low salinity are mixed with the more concentrated introduced saline solution by cc- '.alescence between the particles of the contact material in section 6l immersed in tile continually supplied concentrated saline solution, so that substantially lcomplete nal separation is assured in launder 16 of section 61.

'I'he relatively highly concentrated saline so' lution thus separated is run through line 11 to mix with the cold wet crude oil passing from storage 52 to pump 53 whereby, when the water in the crude oil is of lov;T salinity tending to dilute the saline concentration maintained in section 59, the saline percentage in section 59 is raised with increased eiiiciency in that section.

The second advantage is the saving of salt which may be done, for instance, by running the saline solutions from launders 65 and 15 through pipes 66- and 11, respectively, to one or more evaporating pans 85 andv 86 equipped` with steam coils 81 and 88 to which steam may be supplied through line 89 from heater 55 and' live steam, if required, may additionally be added through line 88.

The saline solution, evaporated to a desired degree of salinity, passes from evaporating pans 85 and 86 through line 8| tor pump 92 which forces it through line 84 into section 16, as described, the relatively high heat of the concentrated solution tending to maintain the desired coalescing temperature in section 16.

In this manner, the loss of salt is avoided and heat losses reducedso as to maintain continuous cyclic operation with low costs in the dehydration of oils.

AIf desired, chemical compounds assisting in the dehydration may be supplied through pipe d il" The process may operate under any desired degree of superatmospheric pressure, depending on the character of the emulsion and the operating temperatures.

The preferred salinity of the body of saline solution containing a 'zone of contact material may range from about to 25% salinity and in general should be greater than the salinity of the contained Water in the oil, although if such salinity of the entering water is sumcient to insure coalescence, the salinity need not be increased.

Simple laboratory trials will determine the required salinity, but in all cases the emulsion Will be passed through a body of water of some degree of salinity while in the presence of the contact material.

I claim as my invention:

1. The process of treating a mixture of oil and water which comprises: maintaining a body of a lsaline solution of sodium chloride containing a zone of nely divided contact material, iowing a stream of undissociated emulsied oil and saline water through said body to effect coalescence of said water with said solution,

and separating the coalesced water after passage through said zone; said saline solution being of the same character as and of a higher concentration than said water.

2. The process of treating a mixture of oil and water which comprises: maintaining a bodyof a saline solution of sodium chloride contain- Aing a zone of -iinely divided contact material, flowing a. stream of undissociated emulsied oil and saline Water through said body to eiect coalescence of said water with said solution, maintaining the salinity of said solution by adding thereto similar salt solution of higher concentration, and separating the coalesced water after passage through saidzone.

3. The process of treating a mixture of oil aware@ and water which comprises: maintaining a body of a saline solution of sodium chloride at about 10% to 25% salinity and containing a zone of finely divided contact material, flowing a stream of undissociated emulsied oil and saline Water through said body to eiect coalescence of said water with said solution, and separating the coalescedwater after passage through said zone; said saline solution being of the same character as and of a higher concentration than said water.

4. The process of treating a mixture of oil and water which comprises: maintaining a body of a saline solution of sodium chloride at about 10% to 25% salinity and containing'a zone of finely divided contact material, iiowing a stream of undissociated emulsied oil and saline water heated to a temperature in excess of 150 F. but below 212 F. through said body to effect coalescence of said water with said solution, and separating the coalesced water after passage through said zone; said saline solution being of the same character as andpi a higher concentration than said water.

5. The process of treating a mixture of water and oil which comprises: maintaining a plurality of bodies of a saline solution of sodium chloride of diierent degrees of salinity` andeach containinga zone of finely divided contact material, iiowing a. stream of undissociated emulsied oil and water heated to a temperature in excess of 150 F. but below the boiling point lof the Water serially through said bodies, separating out coalesced water and solution after passage through each of said zones, and maintaining the salinity of the first body by returning the separated solution from a succeeding body to said iirst body; said rst body being of a higher` saline concentration than the Water originally present in said mixture.

SUMNER E. CAMPBELL. 

